CN112661508A

CN112661508A - Low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material and preparation method thereof

Info

Publication number: CN112661508A
Application number: CN202110071876.5A
Authority: CN
Inventors: 崔斌; 张润; 赵丽丽; 孙芳民; 张小婷; 靳权
Original assignee: Northwestern University
Current assignee: Northwestern University
Priority date: 2021-01-20
Filing date: 2021-01-20
Publication date: 2021-04-16
Anticipated expiration: 2041-01-20
Also published as: CN112661508B

Abstract

The invention discloses a low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material and a preparation method thereof, wherein the ceramic material comprises the chemical composition of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃‑x Na_0.5Bi_0.5TiO₃Wherein x is Na_0.5Bi_0.5TiO₃X is more than or equal to 0.02 and less than or equal to 0.08. The ceramic material prepared by the invention has the maximum value of the dielectric constant 3620 and the maximum value of the energy density 1.72J/cm³. The raw materials used in the invention do not contain lead, have no pollution to the environment, have simple preparation process, good stability and high density, and can meet the requirements of different energy storage applications.

Description

Low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material and preparation method thereof

Technical Field

The invention relates to a low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material and a preparation method thereof, belonging to the technical field of electronic ceramic capacitor materials.

Background

Dielectric ceramic capacitors play a crucial role in power systems due to their excellent environmental suitability, good electrical properties, and ultra-fast charge-discharge rates. However, the device is not suitable for use in a kitchenHowever, the low energy storage density has always limited its application in energy storage. Essentially, the energy storage density is determined by the polarizability (Δ)P) And breakdown field strength (BDS), and therefore researchers have been working primarily on developing materials with large Δ PHigh BDS ceramic materials. Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃It is considered the most promising candidate for ceramic capacitors due to its excellent polarization linearity, but its lower BDS (typically less than 15 kV/mm) and Δ P (possibly less than 10 μ C-cm)^-2) Limiting their use in energy storage devices.

Disclosure of Invention

The invention aims to provide a barium strontium zirconate titanate-based ceramic material which has high delta P value and breakdown field strength and high energy storage through low-temperature sintering and a preparation method thereof.

The invention is realized as follows:

a barium strontium zirconate titanate-based ceramic material, the chemical composition formula of which is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃Wherein x is Na_0.5Bi_0.5TiO₃X is more than or equal to 0.02 and less than or equal to 0.08, and x is preferably 0.04-0.08, and most preferably 0.06.

The preparation method of the barium strontium zirconate titanate-based ceramic material comprises the following steps:

(1) preparation of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃Powder;

(2) preparation of Na_0.5Bi_0.5TiO₃Powder;

(3) according to Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃With Na_0.5Bi_0.5TiO₃The weight ratio is 1: x is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃Powder and Na_0.5Bi_0.5TiO₃Adding absolute ethyl alcohol into the powder for ball milling, and drying to obtain composite powder, wherein x = 0.02-0.08;

(4) after the compound powder is granulated and formed, the compound powder is put intoCalcining at 940-1120 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃A ceramic material.

The step (1) adopts a coprecipitation method to prepare monodisperse micro-nano Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃The powder is specifically as follows: mixing Ba (Ac) according to stoichiometric ratio₂、Sr(Ac)₂、Zr(NO₃)₄·5H₂O and TiCl₄Preparing into solution, firstly, TiCl is added₄Adding the solution into 8-12M sodium hydroxide solution at 20-40 ℃ for hydrolysis for 20-60 min, and then sequentially adding prepared Zr (NO)₃)₄·5H₂O、Sr(Ac)₂And Ba (Ac)₂Reacting the solution for 20-60 min, heating to 80-95 ℃ for reaction, filtering, washing, drying and calcining at 810-890 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃And (3) powder.

In the step (2), Na is prepared by adopting a citric acid self-propagating method_0.5Bi_0.5TiO₃The powder is specifically as follows: weighing Ti (OC) according to stoichiometric ratio₄H₉)₄Adding ethanol to carry out alcoholysis for 5-20 min to form a solution A; weighing Bi (NO) according to the stoichiometric ratio₃)₂·5H₂O and NaNO₃Adding dilute nitric acid to dissolve the nitric acid to form a solution B; finally, mixing the solution A and the solution B to form a solution C; according to Ti (OC)₄H₉)₄、Bi(NO₃)₂·5H₂O and NaNO₃Adding citric acid into the solution C, adjusting the pH of the solution C to 6 by using ammonia water, and continuously stirring to obtain Na, wherein the amount of the citric acid is 1.2-1.5 times of the total molar amount_0.5Bi_0.5TiO₃Sol; the prepared Na_0.5Bi_0.5TiO₃The sol is subjected to self-propagating reaction at 170-190 ℃, and after cooling, grinding and calcining at 650-750 ℃, light yellow Na is obtained_0.5Bi_0.5TiO₃And (3) powder.

In the above step (3), Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃With Na_0.5Bi_0.5TiO₃The weight ratio is 1: (0.04 to 0.08), most preferably 1: 0.06.

in the step (4), the calcination temperature is preferably 980 ℃.

The barium strontium zirconate titanate-based ceramic material prepared by the invention can be used for preparing energy storage devices.

Most of energy storage ceramic materials are prepared by a solid phase method, the sintering temperature is high and is generally over 1300 ℃, so that the phase composition and the morphology of the materials are difficult to control, and the performance is unstable. The inventor finds that the Ba can be treated by the reaction_0.8Sr_0.2Zr_0.1Ti_0.9O₃By carrying out Na_0.5Bi_0.5TiO₃The doping modification method improves the delta P value of the ceramic material to improve the energy storage performance of the material. Theoretically, Ba is added_0.8Sr_0.2Zr_0.1Ti_0.9O₃Doping Na in the base material_0.5Bi_0.5TiO₃The resulting a-site ion inhomogeneity can break the long-range ordered macroscopic domains into short-range ordered polar nano-domains. Due to the low energy barrier and the weak hysteresis effect of the polar nano domains, the relaxivity of the ceramic material can be improved, so that the ceramic material has a higher delta P value. Meanwhile, the grain size of the ceramic is inversely related to the BDS, and it can be seen that a relaxor ferroelectric ceramic having a dense microstructure and a uniform grain size is more likely to have a larger BDS. Therefore, the invention introduces the high-activity Na with small particle size prepared by a chemical method_0.5Bi_0.5TiO₃The powder can reduce the sintering temperature of the ceramic and reduce the sintering energy loss of the ceramic material; but also can obtain fine-grained ceramic materials and improve the microstructure thereof, thereby improving the BDS value of the ceramic materials. Therefore, the low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material can be developed through a polar nano domain structure (polar nano domain engineering) and a fine-grain ceramic material (fine-grain engineering), and has important practical application significance.

The invention prepares a low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material through polar nano domain engineering and fine grain engineering, and the preparation thereofThe preparation principle is as follows: on one hand, the A-site aliovalent cations are utilized to destroy the long-range order of the dipoles of the ferroelectric material, so that the structure of the ferroelectric material on a nanometer scale is uneven, the hysteresis of the polarization strength relative to an electric field is reduced, and the energy storage performance of the material is improved; on the other hand, Na having a small particle diameter is used_0.5Bi_0.5TiO₃The high activity of the powder improves the microstructure of the ceramic and prepares the fine grain ceramic with high breakdown field strength. In addition, Na prepared by citric acid self-propagating method_0.5Bi_0.5TiO₃Has higher activity, thereby reducing the sintering temperature of the ceramic and reducing the energy consumption. The ceramic material prepared according to the invention has a dielectric constant of 3620 at the maximum and an energy density of 1.72J/cm at the maximum³. The raw materials used in the invention do not contain lead, have no pollution to the environment, have simple preparation process, good stability and high density, and can meet the requirements of different energy storage applications.

Drawings

FIG. 1 shows the difference Na_0.5Bi_0.5TiO₃Doping amount of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃An X-ray diffraction pattern of the ceramic;

FIG. 2 shows the difference of Na_0.5Bi_0.5TiO₃Doping amount of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃Surface SEM image of ceramic: (a) x = 0.00; (b) x = 0.02; (c) x = 0.04; (d) x = 0.06; (e) x = 0.08;

FIG. 3 shows the difference Na_0.5Bi_0.5TiO₃Doping amount of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃The variation curve of the average grain size and density of the ceramic;

FIG. 4 shows the difference of Na_0.5Bi_0.5TiO₃Doping amount of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃The dielectric temperature spectrum of the ceramic;

FIG. 5 shows the difference of Na_0.5Bi_0.5TiO₃Doping amount of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃Dielectric loss maps of ceramics;

FIG. 6 is Na_0.5Bi_0.5TiO₃Ba with doping amount of 0.02_0.8Sr_0.2Zr_0.1Ti_0.9O₃—0.02Na_0.5Bi_0.5TiO₃Of ceramicsP—EAn electric hysteresis loop;

FIG. 7 is Na_0.5Bi_0.5TiO₃Ba with doping amount of 0.04_0.8Sr_0.2Zr_0.1Ti_0.9O₃—0.04Na_0.5Bi_0.5TiO₃Of ceramicsP—EAn electric hysteresis loop;

FIG. 8 is Na_0.5Bi_0.5TiO₃Ba with doping amount of 0.06_0.8Sr_0.2Zr_0.1Ti_0.9O₃—0.06Na_0.5Bi_0.5TiO₃Of ceramicsP—EAn electric hysteresis loop;

FIG. 9 is Na_0.5Bi_0.5TiO₃Ba with doping amount of 0.08_0.8Sr_0.2Zr_0.1Ti_0.9O₃—0.08Na_0.5Bi_0.5TiO₃Of ceramicsP—EAnd (4) electric hysteresis loop.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.

Example 1

A low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material comprises a matrix component and a doping component, wherein the chemical formula of the matrix component is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃The chemical formula of the doping component is Na_0.5Bi_0.5TiO₃The chemical composition formula of the barium strontium zirconate titanate-based ceramic material is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃，x=0.02。

(1) first, 5.4 ml of 1.6696 mol/L TiCl were added in a water bath at 30 ℃ with mechanical stirring₄The solution was added dropwise to 100 ml of 10 mol/L sodium hydroxide solution and hydrolyzed for 30 min, after which 2.844 g of Ba (Ac) were weighed out in a stoichiometric ratio₂、0.5021 g Zr(NO₃)₄·5H₂O and 0.5582 g Sr (Ac)₂Respectively adding 20 ml, 10 ml and 10 ml of deionized water to prepare a solution, and sequentially adding the prepared Zr (NO)₃)₄·5H₂O、Sr(Ac)₂And Ba (Ac)₂The solution was added dropwise to TiCl₄Reacting in the sodium hydroxide solution for 30 min, heating the system to 90 ℃ for reacting for 4 h, standing and aging the reaction solution for 24 h after the reaction is finished, pouring out the supernatant, performing suction filtration and washing on the precipitate for multiple times to neutrality, and drying in a 80 ℃ drying oven; calcining the dried reactant at 850 ℃ for 2 h to obtain monodisperse submicron Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃Powder;

(2) weighing 0.0964 g Ti (OC) according to stoichiometric ratio₄H₉)₄Placing into a beaker, adding 2 ml of C₂H₅OH and 1 ml HNO₃Carrying out alcoholysis for 10 min to form solution A; thereafter, 0.0721 g of Bi (NO) were weighed out in turn in the stoichiometric ratio₃)₂·5H₂O、0.0121 g NaNO₃Placing into a B beaker, adding 1 ml of HNO₃And 2 ml of deionized water, and dissolving the deionized water to form a solution B; and finally, fully stirring the solution A and the solution B to form a solution C, adding 0.1488 g of citric acid into the solution C, adjusting the pH =6 of the solution C by using ammonia water, and continuously stirring for 3-4 h to obtain Na_0.5Bi_0.5TiO₃And (3) sol. The prepared Na_0.5Bi_0.5TiO₃Putting the sol in an oven for self-propagating reaction for 3-4 h at 180 ℃, cooling, grinding for 10 min in a mortar, and putting the ground powder in a crucibleCalcining in a crucible at 700 ℃ for 2 h to obtain light yellow Na_0.5Bi_0.5TiO₃Powder;

(3) with Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃As a reference, Na_0.5Bi_0.5TiO₃The doping amount of (A) is 0.02. Weighing 1g of Ba obtained in step (1)_0.8Sr_0.2Zr_0.1Ti_0.9O₃Putting the powder in a ball mill pot, and then adding 0.02 g of Na obtained in the step (2) to the powder_0.5Bi_0.5TiO₃Adding absolute ethyl alcohol into the powder, performing ball milling and mixing for 6 hours, and drying the powder in an oven at 80 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃Composite powder;

(4) the composite powder material is granulated, formed, fired in a muffle furnace, and sintered at 980 ℃ for 2 h to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃The ceramic material is used for testing phase composition, micro morphology, dielectric property and electric hysteresis loop.

A sample of the ceramic material obtained in example 1, the phase composition of which was analyzed (see fig. 1); observing the microscopic morphology (see fig. 2); the average particle size of the ceramic was calculated using Nano measure, and the density of the ceramic was calculated using Archimedes drainage method (see FIG. 3); testing the dielectric property of the material to obtain a dielectric temperature spectrum (see figure 4) and a dielectric loss graph (see figure 5); the energy storage performance was tested (see fig. 6).

These test results show that the ceramic material obtained in this example is mainly of perovskite structure, the particle size of the ceramic is about 205 nm, the maximum dielectric constant is 2290, and the dielectric loss is about 0.1072; the polarization difference is 10 μ C ∙ cm^-2Breakdown field strength of 12.01 kV/mm, 1.52J/cm³And an energy storage efficiency of 43%.

Example 2

A low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material is composed of a matrix component and a doping componentThe chemical formula of the matrix component is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃The chemical formula of the doping component is Na_0.5Bi_0.5TiO₃The chemical composition formula of the low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃，x=0.04。

The preparation method of the low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material comprises the following steps of:

(2) weighing 0.0964 g Ti (OC) according to stoichiometric ratio₄H₉)₄Placing into a beaker, adding 2 ml of C₂H₅OH and 1 ml HNO₃Carrying out alcoholysis for 10 min to form solution A; thereafter, 0.0721 g of Bi (NO) were weighed out in turn in the stoichiometric ratio₃)₂·5H₂O、0.0121 g NaNO₃Placing into another beaker, adding 1 ml HNO₃And 2 ml of deionized water, and dissolving the deionized water to form a solution B; finally, fully stirring the solution A and the solution B to formAdding 0.1488 g of citric acid into the solution C, adjusting the pH =6 of the solution C by ammonia water, and continuously stirring for 3-4 h to obtain Na_0.5Bi_0.5TiO₃And (3) sol. The prepared Na_0.5Bi_0.5TiO₃Putting the sol in a drying oven for self-propagating reaction for 3-4 h at 180 ℃, cooling, grinding in a mortar for 10 min, putting the ground powder in a crucible, and calcining for 2 h at 700 ℃ to obtain light yellow Na_0.5Bi_0.5TiO₃Powder;

(3) with Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃As a reference, Na_0.5Bi_0.5TiO₃The doping amount of (3) was 0.04. Weighing 1g of Ba obtained in step (1)_0.8Sr_0.2Zr_0.1Ti_0.9O₃Putting the powder in a ball mill pot, and adding 0.04 g of Na obtained in the step (2) into the ball mill pot_0.5Bi_0.5TiO₃Adding absolute ethyl alcohol into the powder, performing ball milling and mixing for 6 hours, and drying the powder in an oven at 80 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—Na_0.5Bi_0.5TiO₃Composite powder;

(4) the composite powder material is granulated, formed, fired in a muffle furnace, and sintered at 980 ℃ for 2 h to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—Na_0.5Bi_0.5TiO₃The ceramic material is used for testing phase composition, micro morphology, dielectric property and electric hysteresis loop.

A sample of the ceramic material obtained in example 2, the phase composition of which was analyzed (see fig. 1); observing the microscopic morphology (see fig. 2); the average particle size of the ceramic was calculated using Nano measure, and the density of the ceramic was calculated using Archimedes drainage method (see FIG. 3); testing the dielectric property of the material to obtain a dielectric temperature spectrum (see figure 4) and a dielectric loss graph (see figure 5); the energy storage performance was tested (see fig. 7).

These test results show that the ceramic material obtained in this example is mainly of perovskite structure, the particle size of the ceramic is about 210 nm, and the maximum dielectric constant2860, dielectric loss of about 0.0245; polarization difference is 13 μ C ∙ cm^-2The breakdown field intensity is 16.03 kV/mm and is 1.63J/cm³Energy storage density and energy storage efficiency of 55%.

Example 3

A low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material comprises a matrix component and a doping component, wherein the chemical formula of the matrix component is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃The chemical formula of the doping component is Na_0.5Bi_0.5TiO₃The chemical composition formula of the low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃，x=0.06。

(1) first, 5.4 ml of 1.6696 mol/L TiCl were added in a water bath at 30 ℃ with mechanical stirring₄The solution was added dropwise to 100 ml of 10 mol/L sodium hydroxide solution and hydrolyzed for 30 min, after which 2.844 g of Ba (Ac) were weighed out in a stoichiometric ratio₂、0.5021 g Zr(NO₃)₄·5H₂O and 0.5582 g Sr (Ac)₂Respectively adding 20 ml, 10 ml and 10 ml of deionized water to prepare a solution, and sequentially adding the prepared Zr (NO)₃)₄·5H₂O、Sr(Ac)₂And Ba (Ac)₂The solution was added dropwise to TiCl₄Reacting in the sodium hydroxide solution for 30 min, heating the system to 90 ℃ for reacting for 4 h, standing and aging the reaction solution for 24 h after the reaction is finished, pouring out the supernatant, performing suction filtration and washing on the precipitate for multiple times to neutrality, and drying in a 80 ℃ drying oven; calcining the dried reactant at 850 ℃ for 2 h to obtain monodisperse submicron Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃And (3) powder.

(2) Weighing 0.0964 g Ti (OC) according to stoichiometric ratio₄H₉)₄Placing into a beaker, adding 2 ml of C₂H₅OH and 1 ml HNO₃Carrying out alcoholysis for 10 min to form solution A; thereafter, 0.0721 g of Bi (NO) were weighed out in turn in the stoichiometric ratio₃)₂·5H₂O、0.0121 g NaNO₃Placing into another beaker, adding 1 ml HNO₃And 2 ml of deionized water, and dissolving the deionized water to form a solution B; and finally, fully stirring the solution A and the solution B to form a solution C, adding 0.1488 g of citric acid into the solution C, adjusting the pH =6 of the solution C by using ammonia water, and continuously stirring for 3-4 h to obtain Na_0.5Bi_0.5TiO₃And (3) sol. The prepared Na_0.5Bi_0.5TiO₃Putting the sol in a drying oven for self-propagating reaction for 3-4 h at 180 ℃, cooling, grinding in a mortar for 10 min, putting the ground powder in a crucible, and calcining for 2 h at 700 ℃ to obtain light yellow Na_0.5Bi_0.5TiO₃And (3) powder.

(3) With Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃As a reference, Na_0.5Bi_0.5TiO₃The doping amount of (3) is 0.06. Weighing 1g of Ba obtained in step (1)_0.8Sr_0.2Zr_0.1Ti_0.9O₃Putting the powder in a ball mill pot, and then adding 0.06 g of Na obtained in the step (2) to the powder_0.5Bi_0.5TiO₃Adding absolute ethyl alcohol into the powder, performing ball milling and mixing for 6 hours, and drying the powder in an oven at 80 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃Composite powder;

A sample of the ceramic material obtained in example 3, the phase composition of which was analyzed (see fig. 1); observing the microscopic morphology (see fig. 2); the average grain size of the ceramic is calculated by using Nano measure, and the density of the ceramic is calculated by using an Archimedes drainage method (see figure 3); testing the dielectric property of the material to obtain a dielectric temperature spectrum (see figure 4) and a dielectric loss graph (see figure 5); the energy storage performance was tested (see fig. 8).

These test results show that the ceramic material obtained in this example is mainly of perovskite structure, the particle size of the ceramic is about 210 nm, the maximum dielectric constant is 3620, and the dielectric loss is about 0.0138; the polarization difference is 18 mu C ∙ cm^-2The breakdown field strength is 18.09 kV/mm and is 1.72J/cm³And an energy storage efficiency of 79%.

Example 4

A low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material comprises a matrix component and a doping component, wherein the chemical formula of the matrix component is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃The chemical formula of the doping component is Na_0.5Bi_0.5TiO₃The chemical composition formula of the low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃，x=0.08。

(1) first, 5.4 ml of 1.6696 mol/L TiCl were added in a water bath at 30 ℃ with mechanical stirring₄The solution was added dropwise to 100 ml of 10 mol/L sodium hydroxide solution and hydrolyzed for 30 min, after which 2.844 g Ba (Ac) was weighed out in the stoichiometric ratio₂、0.5021 g Zr(NO₃)₄·5H₂O and 0.5582 g Sr (Ac)₂Respectively adding 20 ml, 10 ml and 10 ml of deionized water to prepare a solution, and sequentially adding the prepared Zr (NO)₃)₄·5H₂O、Sr(Ac)₂And Ba (Ac)₂Solution to TiCl₄Reacting in sodium hydroxide solution for 30 min, heating the system to 90 ℃ for reacting for 4 h, standing and aging the reaction solution for 24 h after the reaction is finished, aging the reaction solution for 12 h after the reaction is completed, filtering, and precipitating with distilled waterWashing for many times until the solution is neutral, and drying in an oven at 80 ℃; calcining the dried precipitate at 850 ℃ for 2 h to obtain monodisperse submicron Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃Powder;

(3) With Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃As a reference, Na_0.5Bi_0.5TiO₃The doping amount of (A) is 0.08. Weighing 1g of Ba obtained in step (1)_0.8Sr_0.2Zr_0.1Ti_0.9O₃Putting the powder in a ball mill pot, and then adding 0.02 g of Na obtained in the step (2) to the powder_0.5Bi_0.5TiO₃Adding absolute ethyl alcohol into the powder, performing ball milling and mixing for 6 hours, and drying the powder in an oven at 80 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃Composite powder;

A sample of the ceramic material obtained in example 4, the phase composition of which was analyzed (see fig. 1); observing the microscopic morphology (see fig. 2); the average particle size of the ceramic was calculated using Nano measure, and the density of the ceramic was calculated using Archimedes drainage method (see FIG. 3); testing the dielectric property of the material to obtain a dielectric temperature spectrum (see figure 4) and a dielectric loss graph (see figure 5); the energy storage performance was tested (see fig. 9).

These test results show that the ferroelectric ceramic material obtained in this example is superior to Na_0.5Bi_0.5TiO₃And Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃The solid solubility of the two materials shows impurity phase, which causes the phenomenon of excessive growth of the crystal grains of the ceramic, the grain diameter of the ceramic is about 400 nm, the maximum dielectric constant is 3317, and the dielectric loss is about 0.0282; the polarization difference is 16 mu C ∙ cm^-2The breakdown field strength is 17.04 kV/mm and is 1.56J/cm³And an energy storage efficiency of 71%.

Example 5

Similar to example 3, except that only the sintering temperature was changed, the sintering temperature was 940 ℃; the composition formula and the preparation conditions are unchanged. The test result shows that the ceramic material obtained in the embodiment is mainly of a perovskite structure, the particle size of the ceramic is about 215 nm, the maximum dielectric constant is 1308, and the dielectric loss is about 0.1504; the polarization difference of the ceramic material is 11 mu C ∙ cm^-2The breakdown field strength is 15.99 kV/mm, and the breakdown field strength is 0.96J/cm³Energy storage density and energy storage efficiency of 55%.

Example 6

Similar to example 3, except that the sintering temperature was changed, the sintering temperature was 1120 ℃, and the composition formulation and preparation conditions were not changed. The test results show that the ceramic material obtained in this example is Na⁺And Bi³⁺The ions are easy to volatilize in the high-temperature sintering process, the chemical composition deviates, and a small amount of impure phase appears in XRDResulting in a slight reduction in energy storage density. The grain size of the ceramic is about 430 nm, the maximum dielectric constant is 2310, and the dielectric loss is about 0.0989; the polarization difference is 14 μ C ∙ cm^-2The breakdown field strength is 19.53 kV/mm and is 1.23J/cm³And an energy storage efficiency of 72%.

Claims

1. A barium strontium zirconate titanate-based ceramic material is characterized in that: the chemical composition formula of the barium strontium zirconate titanate-based ceramic material is Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃Wherein x is Na_0.5Bi_0.5TiO₃X is more than or equal to 0.02 and less than or equal to 0.08.

2. A barium strontium zirconate titanate-based ceramic material according to claim 1, wherein: x is more than or equal to 0.04 and less than or equal to 0.08.

3. A method for preparing a barium strontium zirconate titanate-based ceramic material according to claim 1, comprising the steps of:

(1) preparation of Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃Powder;

(2) preparation of Na_0.5Bi_0.5TiO₃Powder;

(4) after granulating and forming the composite powder, calcining at 940-1120 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃—x Na_0.5Bi_0.5TiO₃A ceramic material.

4. The method for preparing a barium strontium zirconate titanate-based ceramic material according to claim 3, wherein: step (1) preparing monodisperse micro-nano Ba by adopting a coprecipitation method_0.8Sr_0.2Zr_0.1Ti_0.9O₃And (3) powder.

5. The method for preparing barium strontium zirconate titanate-based ceramic material according to claim 4, wherein Ba is added_0.8Sr_0.2Zr_0.1Ti_0.9O₃The preparation method of the powder comprises the following steps: mixing Ba (Ac) according to stoichiometric ratio₂、Sr(Ac)₂、Zr(NO₃)₄·5H₂O and TiCl₄Preparing into solution, firstly, TiCl is added₄Adding the solution into 8-12M sodium hydroxide solution at 20-40 ℃ for hydrolysis for 20-60 min, and then sequentially adding prepared Zr (NO)₃)₄·5H₂O、Sr(Ac)₂And Ba (Ac)₂Reacting the solution for 20-60 min, heating to 80-95 ℃ for reaction, filtering, washing, drying and calcining at 810-890 ℃ to obtain Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃And (3) powder.

6. The method for preparing a barium strontium zirconate titanate-based ceramic material according to claim 3, wherein Na is prepared by citric acid self-propagating method in step (2)_0.5Bi_0.5TiO₃And (3) powder.

7. The method for preparing a barium strontium zirconate titanate-based ceramic material according to claim 6, wherein Na is added_0.5Bi_0.5TiO₃The preparation method of the powder comprises the following steps: weighing Ti (OC) according to stoichiometric ratio₄H₉)₄Adding ethanol to carry out alcoholysis for 5-20 min to form a solution A; weighing Bi (NO) according to the stoichiometric ratio₃)₂·5H₂O and NaNO₃Adding dilute nitric acid to dissolve the nitric acid to form a solution B; finally, mixing the solution A and the solution B to form a solution C; according to Ti (OC)₄H₉)₄、Bi(NO₃)₂·5H₂O and NaNO₃Adding citric acid into the solution C, adjusting the pH of the solution C to 6 by using ammonia water, and continuously stirring to obtain Na, wherein the amount of the citric acid is 1.2-1.5 times of the total molar amount_0.5Bi_0.5TiO₃Sol; the prepared Na_0.5Bi_0.5TiO₃The sol is subjected to self-propagating reaction at 170-190 ℃, and after cooling, grinding and calcining at 650-750 ℃, light yellow Na is obtained_0.5Bi_0.5TiO₃And (3) powder.

8. The method for preparing barium strontium zirconate titanate-based ceramic material according to claim 3, wherein Ba is added in step (3)_0.8Sr_0.2Zr_0.1Ti_0.9O₃With Na_0.5Bi_0.5TiO₃The weight ratio is 1: 0.06.

9. the method for preparing a barium strontium zirconate titanate-based ceramic material according to claim 3, wherein the calcination temperature in step (4) is 980 ℃.

10. Use of a barium strontium zirconate titanate-based ceramic material according to claim 1 for the preparation of energy storage devices.